CN101205348B - Urea-formaldehyde resin additive, urea-formaldehyde resin containing the same and preparation method thereof - Google Patents

Urea-formaldehyde resin additive, urea-formaldehyde resin containing the same and preparation method thereof Download PDF

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Publication number
CN101205348B
CN101205348B CN2007101792173A CN200710179217A CN101205348B CN 101205348 B CN101205348 B CN 101205348B CN 2007101792173 A CN2007101792173 A CN 2007101792173A CN 200710179217 A CN200710179217 A CN 200710179217A CN 101205348 B CN101205348 B CN 101205348B
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urea
formaldehyde resin
additive
complexing agent
preparation
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CN101205348A (en
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李建章
周文瑞
张世锋
母军
张德荣
高强
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Changzhou Joel Plastic Co., Ltd.
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Beijing Forestry University
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Abstract

The invention provides an additive with urea formaldehyde, a preparation method and a urea formaldehyde resin adhesive. The additive is provided by the invention. The raw material of the additive is comprised of the dispersion medium, the dried egg white of the degreased bean and the complexing agent, the weight ratio of the raw material is: 70-80 of dispersion medium, 20-35 of dried egg white of the degreased bean, 1-3 of complexing agent, the complexing agent is consisted of the aluminium sulphate and the zirconium carbonate with the weight ratio of 0.4-2.4:1. The additive provided by the invention contains dried egg white of the degreased bean, and then both the bond strength of the prepared veneer is increased and the formaldehyde emission of the preparing artificial slabs is effective decreased when adding the additive into the urea formaldehyde.

Description

The additive of urea-formaldehyde resin, contain urea-formaldehyde resin of this additive and preparation method thereof
Technical field
The present invention relates to a kind of tackiness agent additive, contain this additive based on tackiness agent of organic high molecular compound and preparation method thereof, particularly a kind of wood-based plate with the additive of urea-formaldehyde resin, contain urea-formaldehyde resin of this additive and preparation method thereof.
Background technology
Over 30 years, the timber industry of China has obtained fast development.2006, wood-based plate ultimate production 7428 ten thousand steres, wherein glued board 2729 ten thousand steres, core-board 1155 ten thousand steres.Wood-based plate ultimate production, glued board output, furniture output all occupy the No. 1 in the world.
Because what generally adopt in the Wood-based Panel Production is that formaldehyde is tackiness agent, particularly use urea-formaldehyde resin adhesive in a large number, causing wood-based plate and goods thereof (furniture, timber floor, indoor wooden decorative material etc.) to exist formaldehyde and discharge problem, is the main source that formaldehyde pollutes in the room air pollution.
Along with the raising day by day of health of people consciousness, indoor environment consciousness, quality of life consciousness, artificial board formaldehyde discharges the polluted air, the problem that impairs one's health that cause and more and more is subject to people's attention.City in China, after " coal smoke type ", " photo-chemical smog type " polluted, the modern was just fallen into the 3rd pollution period that with " room air pollution " is sign.A Beijing City indoor pollution quality testing is surveyed the result and is shown, the room air pollution degree than outdoor high 4-8 doubly; The mean concns that is called as the formaldehyde of one of " four big stealthy killers " exceeds standard 6-7 doubly.Formaldehyde has hormesis to eye, mucous membrane and respiratory tract, can cause chronic respiratory tract disease, allergic rhinitis, lower immune function etc.; Being considered to the potential carcinogenic substance, may be the inducement of rhinocarcinoma, laryngocarcinoma, skin carcinoma.According to statistics, the death toll that exceeds the quata that China is caused by room air pollution every year reaches 11.1 ten thousand people, several 220,000 person-times of the outpatient service that exceeds the quata, several 4,300,000 person-times of the emergency treatment that exceeds the quata.Solve artificial board formaldehyde release problem and arrived instant stage.
At present, the method for reduction artificial board formaldehyde burst size mainly contains: 1) adopt low mol ratio modified urea-formaldehyde resin adhesive; 2) adopt other environmental-protection type adhesives; 3) add formaldehyde-trapping agent at wood-based plate in urea-formaldehyde resin adhesive; 4) wood-based plate is carried out aftertreatment.But these technological methods all exist such or such defective.As, 1) though adopt low mol ratio modified urea-formaldehyde resin adhesive can effectively reduce the burst size of methanal of wood-based panel product, the bonding strength of product also often reduces, and can not meet the demands; Prolong set time, and production efficiency reduces; 2) adopt other environmental-protection type adhesives, as the isocyanates tackiness agent, cause the production cost of wood-based plate often to increase considerably, enterprise and user are difficult to accept; 3) add formaldehyde-trapping agent at wood-based plate in urea-formaldehyde resin adhesive,, often reduce the bonding strength of wood-based plate simultaneously though can effectively reduce the free formaldehyde in artificial plate burst size; Simultaneously, general formaldehyde-trapping agent price often is higher than urea-formaldehyde resin adhesive far away, its adding has just improved product cost, reduced product competitiveness, for example the FC-5 formaldehyde-trapping agent price of the big deer development Co., Ltd. of Japan production is 50000 yuan/ton, if add 1%-2% in glue, urea-formaldehyde resin cost then per ton will improve 500~1000 yuan; 4) wood-based plate is carried out aftertreatment, it as publication number the manufacturing process that discloses a kind of E1/E0 level environment friendly artificial board in the application for a patent for invention of CN1526528, adopt the ammonia vacuum method, publication number is to disclose a kind of treatment unit that reduces artificial board formaldehyde burst size in the utility model patent of CN2394770, and is bigger but finishing apparatus is often invested.
Summary of the invention
The objective of the invention is the problem that exists at above prior art, a kind of additive, its preparation method of adhesion agent for artificial board is provided and contains the urea-formaldehyde resin of this additive.Contain degreasing soybean protein powder in the additive of the present invention, in urea-formaldehyde resin, add this additive, not only guarantee the bonding strength of prepared glued board, and can effectively reduce the burst size of methanal in the prepared glued board.
For realizing purpose of the present invention, one aspect of the present invention provides a kind of additive of urea-formaldehyde resin, and its raw material comprises dispersion medium, degreasing soybean protein powder and complexing agent.
Wherein, the weight part proportioning of above-mentioned raw materials is: dispersion medium 70-80, degreasing soybean protein powder 20-35, complexing agent 1-3.Particularly, the weight part proportioning of raw material is selected dispersion medium 72-76, degreasing soybean protein powder 25-30, complexing agent 1.2-2.6.
Wherein, dispersion medium is chosen as softening water.
Wherein, complexing agent comprises Tai-Ace S 150 and zirconium carbonate, and the weight part proportioning between Tai-Ace S 150 and the zirconium carbonate is: 0.4-2.4: 1, and preferred 0.6-1.8: 1.
The present invention provides a kind of preparation method of additive of urea-formaldehyde resin on the other hand, comprises following step in sequence: degreasing soybean protein powder is dispersed in the dispersion medium; 2) adding complexing agent makes it carry out complex reaction.
Wherein, in described step 1), stir after degreasing soybean protein powder added described dispersion medium, and the mixture that makes acquisition is 40-80 ℃ of insulation 3-6 hour down; In described step 2) in, add complexing agent when making described mixture be cooled to 25-35 ℃ and stir.
Wherein, the weight part proportioning of raw material is: dispersion medium: 70-80, degreasing soybean protein powder 20-35, complexing agent 1-3.Particularly, the weight part proportioning of raw material is selected: dispersion medium 72-76, degreasing soybean protein powder 25-30, complexing agent 1.2-2.6.
Wherein, complexing agent comprises Tai-Ace S 150 and zirconium carbonate, and the weight part proportioning between Tai-Ace S 150 and the zirconium carbonate is: 0.4-2.4: 1, and preferred 0.6-1.8: 1.
Wherein, dispersion medium is chosen as softening water.
The present invention provides a kind of urea-formaldehyde resin adhesive on the other hand, contains the additive of above-mentioned urea-formaldehyde resin.
Wherein, the weight part proportioning of the additive of urea-formaldehyde resin and urea-formaldehyde resin is 0.25-4: 1.
Particularly, urea-formaldehyde resin selection urea and formaldehyde mole ratio are 1: the urea-formaldehyde resin of 1.1-2.0.
Advantage applies of the present invention is in the following areas:
1, the degreasing soybean protein is a kind of reproducible resource; raw material as adhesion agent for artificial board; help to solve the exhausted problem of the synthetic fossil feedstock of using in the conventional adhesive of artificial board; the fossil resource consumption in the urea-formaldehyde resin manufacturing be can effectively save, environment protection and continuable development principle met.
2, the urea-formaldehyde resin of the present invention's preparation can not reduce under urea formaldehyde resin adhesive curing speed, the bonding strength prerequisite in assurance, reduces the burst size of methanal that glueds joint goods greatly.
3, the additive of the inventive method and to contain the preparation method of urea-formaldehyde resin of additive simple, the processing condition gentleness, easy and simple to handle, final product quality is controlled easily, and production cost is low.
Embodiment
Describe content of the present invention in detail below by specific embodiment.
It is 1: 1.2 urea-formaldehyde resin that the present invention adopts the mol ratio of urea and formaldehyde, and the performance index of urea-formaldehyde resin are as follows:
Solids content 50-55%
PH value 7.0-7.2
Viscosity (20 ℃) 150-300mPas
Free formaldehyde content<0.3%
20-30 days storage period
The urea-formaldehyde resin that the present invention uses is not limited to above-mentioned urea-formaldehyde resin, and various common urea-formaldehyde resin and modified urea-formaldehyde resin that factory generally adopts also all are suitable for.
Embodiment 1
The additive of urea-formaldehyde resin of the present invention is according to following steps production:
1) get the raw materials ready according to following weight proportion:
Softening water 70kg
Degreasing soybean protein powder 20kg
Tai-Ace S 150 0.8kg
Zirconium carbonate 0.5kg
2) whole degreasing soybean protein powder addings is equipped with in the reactor of softening water, stirs;
3) heat temperature raising to 40 ℃, insulation reaction 6 hours;
4) be cooled to 30 ℃ then, order adds Tai-Ace S 150, zirconium carbonate in reactor, stirs, and makes the soybean protein additive.
Wherein, the performance index of soybean protein additive are as shown in table 1.
Modified urea-formaldehyde resin tackiness agent in the present embodiment is formulated in the following manner: the soybean protein additive is more even than the mixed that is 30: 70 by weight with above-mentioned urea-formaldehyde resin.
The quality index of the modified urea-formaldehyde resin tackiness agent of preparation is as shown in table 2.
Embodiment 2
The additive of urea-formaldehyde resin of the present invention is according to following steps production:
1) get the raw materials ready according to following weight proportion:
Softening water 80kg
Degreasing soybean protein powder 35kg
Tai-Ace S 150 1.0kg
Zirconium carbonate 1.5kg
2) whole degreasing soybean protein powder addings is equipped with in the reactor of softening water, stirs;
3) heat temperature raising to 50 ℃, insulation reaction 3 hours;
4) be cooled to 30 ℃ then, order adds Tai-Ace S 150, zirconium carbonate in reactor, stirs, and makes the soybean protein additive.
Wherein, the performance index of soybean protein additive are as shown in table 1.
Modified urea-formaldehyde resin tackiness agent in the present embodiment is formulated in the following manner: the soybean protein additive is more even than the mixed that is 50: 50 by weight with above-mentioned urea-formaldehyde resin.
The quality index of the modified urea-formaldehyde resin tackiness agent of preparation is as shown in table 2.
Embodiment 3
The additive of urea-formaldehyde resin of the present invention is according to following steps production:
1) get the raw materials ready according to following weight proportion:
Softening water 75kg
Degreasing soybean protein powder 30kg
Tai-Ace S 150 1.1kg
Zirconium carbonate 1.2kg
2) whole degreasing soybean protein powder addings is equipped with in the reactor of softening water, stirs;
3) heat temperature raising to 60 ℃, insulation reaction 5 hours;
4) be cooled to 30 ℃ then, order adds Tai-Ace S 150, zirconium carbonate in reactor, stirs, and makes the soybean protein additive.
Wherein, the performance index of soybean protein additive are as shown in table 1.
The modified urea-formaldehyde resin tackiness agent is formulated in the following manner in the present embodiment: the soybean protein additive is more even than the mixed that is 70: 30 by weight with above-mentioned urea-formaldehyde resin.
The quality index of the modified urea-formaldehyde resin tackiness agent of preparation is as shown in table 2.
The performance index detected result of table 1 soybean protein additive of the present invention
Outward appearance The pH value Solids content (%)
Embodiment 1 Yellow mucus 6.0-7.0 22-28
Embodiment 2 Yellow mucus 6.0-7.0 25-30
Embodiment 3 Yellow mucus 6.0-7.0 25-30
The capability and performance index detected result of table 2 modified urea-formaldehyde resin tackiness agent of the present invention
The pH value Solids content (%) Viscosity (20 ℃) (mPas) Free formaldehyde content (%) Storage period (my god)
Embodiment 1 6.0-7.2 40-52 150-400 <0.2 20
Embodiment 2 6.0-7.2 40-52 150-400 <0.2 20
Embodiment 3 7.0-7.2 50-55 150-400 <0.2 20
Reference examples 1
The mol ratio that adopts above-mentioned urea and formaldehyde is 1: 1.2 a urea-formaldehyde resin example 1 in contrast.
Experimental example 1
Utilize the modified urea-formaldehyde resin adhesive of the embodiment of the invention and the tackiness agent of reference examples 1-2 to make seven layers of glued board respectively, adopt following preparation technology parameter:
Board using poplar board: water ratio 5~8%; Thick 1.6mm;
Impregnation: add flour by 10% of gross weight in each glue, be in harmonious proportion evenly;
Applying glue: central layer double spread, Amount of spread are 220~300g/m 2
Ageing mode and time: closed ageing, ageing 30 minutes.
Preload pressure and time: pressure 0.8MPa, precompressed 30 minutes.
Hot pressing: hot pressing pressure 1.2MPa, hot pressing temperature is 120 ℃, hot pressing time is 3min.
The performance test results of seven layers of glued board making by above-mentioned technology is as shown in table 3, wherein by GB/T17657-1999 " wood-based plate and face artificial board physicochemical property experimental technique " detection method the glued board product of production is carried out Performance Detection.
The burst size of methanal of table 3 glued board and bonding strength
Test specimen Burst size of methanal (mg/L) Bonding strength (MPa)
Embodiment 1 0.46 1.17
Embodiment 2 0.32 1.09
Embodiment 3 0.15 0.98
Reference examples 1 1.02 1.13
Experimental result shows, adopt that burst size of methanal significantly reduces in the glued board of modified urea-formaldehyde resin adhesive of the present invention preparation, compare with burst size of methanal in the glued board of reference examples 1 tackiness agent preparation, the burst size of methanal of embodiment 1-3 has descended 55.9%, 68.6% and 85.3% respectively.Therefore, adopt the degreasing soybean protein additive of the inventive method preparation to mix use with urea-formaldehyde resin, can effectively reduce the burst size of methanal that glueds joint goods.
In addition, experimental result shows, after adopting the soybean glue stick additive for preparing through the present invention to mix (the weight part proportioning is below 70%) with urea-formaldehyde resin, the bonding property urea formaldehyde resin adhesive suitable can be obtained, the bonding strength of glued board can be guaranteed with common urea-formaldehyde resin.
The regulation that the glued board of the modified urea-formaldehyde resin adhesive preparation of the inventive method preparation is pressed GB/T17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " reaches II class glued board gummed intensity.
The burst size of methanal and the physical and mechanical property index request of II class glued board are as follows: E1 level, burst size of methanal≤1.5mg/L; The E2 level, burst size of methanal≤5.0mg/L; Poplar plywood bonding strength 〉=0.7MPa.The detected result of table 3 illustrates that also modified urea-formaldehyde resin adhesive of the present invention is little to the physical and mechanical property influence of glued board, does not reduce the grade of glued board.

Claims (5)

1. the preparation method of the additive of a urea-formaldehyde resin comprises following step in sequence:
1) gets the raw materials ready according to following weight part proportioning: dispersion medium: 70-80, degreasing soybean protein powder 20-35, complexing agent 1-3, wherein, described dispersion medium is a softening water, and described complexing agent comprises Tai-Ace S 150 and zirconium carbonate, and the weight part proportioning between Tai-Ace S 150 and the zirconium carbonate is: 0.4-2.4: 1;
2) degreasing soybean protein powder is dispersed in the dispersion medium, stirs, make the mixture of acquisition be incubated 3-6 hour down at 40-80 ℃;
Add described complexing agent when 3) mixture is cooled to 25-35 ℃ and stir, carry out complex reaction.
2. the preparation method of the additive of urea-formaldehyde resin as claimed in claim 1 is characterized in that the weight part proportioning of described raw material is selected: dispersion medium 72-76, degreasing soybean protein powder 25-30, complexing agent 1.2-2.6.
3. the preparation method of the additive of urea-formaldehyde resin as claimed in claim 1 or 2 is characterized in that the weight part proportioning between the Tai-Ace S 150 and zirconium carbonate is in the described complexing agent: 0.6-1.8: 1.
4. the additive of a urea-formaldehyde resin is characterized in that being prepared from according to claim 1 to 3 either party method.
5. a urea-formaldehyde resin adhesive is characterized in that containing urea-formaldehyde resin additive as claimed in claim 4, and wherein, the weight part proportioning of additive and urea-formaldehyde resin is 0.25-4: 1.
CN2007101792173A 2007-12-11 2007-12-11 Urea-formaldehyde resin additive, urea-formaldehyde resin containing the same and preparation method thereof Active CN101205348B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592920A (en) * 2015-02-09 2015-05-06 金思思 Urea-formaldehyde adhesive and preparation method thereof
CN106634746A (en) * 2016-12-17 2017-05-10 浦北县建业胶合板有限责任公司 Urea resin additive and preparation method thereof
CN110216747A (en) * 2019-05-31 2019-09-10 千年舟新材科技集团有限公司 Water proof particleboard and its preparation process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4942191A (en) * 1988-04-25 1990-07-17 Borden, Inc. Aldehyde condensation resin glue compositions having pea and other leguminous flour extenders
CN1818000A (en) * 2006-03-22 2006-08-16 北京林业大学 Additive of phenolic resin, phenolic resin therewith and production thereof
CN1962800A (en) * 2006-11-22 2007-05-16 山东万得福实业集团有限公司 Process for producing soyabean protein adhesive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4942191A (en) * 1988-04-25 1990-07-17 Borden, Inc. Aldehyde condensation resin glue compositions having pea and other leguminous flour extenders
CN1818000A (en) * 2006-03-22 2006-08-16 北京林业大学 Additive of phenolic resin, phenolic resin therewith and production thereof
CN1962800A (en) * 2006-11-22 2007-05-16 山东万得福实业集团有限公司 Process for producing soyabean protein adhesive

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Patentee before: Beijing Forestry University