CN1817932A - Urea resin and production thereof - Google Patents
Urea resin and production thereof Download PDFInfo
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- CN1817932A CN1817932A CN 200610059843 CN200610059843A CN1817932A CN 1817932 A CN1817932 A CN 1817932A CN 200610059843 CN200610059843 CN 200610059843 CN 200610059843 A CN200610059843 A CN 200610059843A CN 1817932 A CN1817932 A CN 1817932A
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Abstract
A urea resin and its production are disclosed. The procedure is carried out by taking low-mol ratio methyl aldehyde and urea as raw materials, adding urea into methyl aldehyde by 4 times, activating methyl aldehyde at 50+-5 degrees C for 15-25mins before adding urea for first time, and adding into ammonia water to have rear-treatment after adding urea for fourth time to obtain final product. It is simple and cheap, has no any modifier and dewatering.
Description
Technical field
The present invention relates to a kind of urea-formaldehyde resin and preparation method thereof, relate in particular to a kind of wood-based plate urea-formaldehyde resin and preparation method thereof.
Background technology
Along with improving constantly of living standards of the people, decorations, purchase new furniture and become usual thing in the people life.All kinds of wood-based plates of often a large amount of uses during decorations and furniture are made, as glued board, core-board, medium density fibre board (MDF), shaving board etc., and these wood-based plates mostly are to use formaldehyde is tackiness agent, mainly be that the urea-formaldehyde resin adhesive ubiquity formaldehyde release problem, usually become the arch-criminal who causes formaldehyde in indoor air to pollute.
Formaldehyde is more highly toxic material, preferentially controls on the list formaldehyde at China's noxious chemical and is in second.Formaldehyde has hormesis to eye, mucous membrane and respiratory tract, can cause chronic respiratory tract disease, allergic rhinitis, lower immune function etc., causes sleep disorder; Formaldehyde is considered to the potential carcinogenic substance, may be the inducement of rhinocarcinoma, laryngocarcinoma, skin carcinoma.Therefore, eliminate formaldehyde and pollute, purifying the air of a room more and more causes people's attention.
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; And the adhesive solidification time lengthening, production efficiency reduces; 2) adopt other environmental-protection type adhesives, as the isocyanates tackiness agent, the production cost of wood-based plate often increases considerably, and 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; In addition, the price of general formaldehyde-trapping agent often is higher than urea-formaldehyde resin adhesive far away, and its adding has improved product cost, has reduced competitiveness of product; 4) wood-based plate is carried out aftertreatment, be that the manufacturing process that discloses a kind of E1/EO level environment friendly artificial board in the application for a patent for invention of CN1526528A adopts the ammonia vacuum method as publication number, publication number is to disclose a kind of treatment unit that reduces artificial board formaldehyde burst size in the utility model patent of CN2394770Y, though these measures can effectively reduce the free formaldehyde in artificial plate burst size, finishing apparatus is often invested bigger.
Summary of the invention
The objective of the invention is problem at the prior art existence, a kind of wood-based plate urea-formaldehyde resin and preparation method thereof is provided, it is raw material that this method adopts the formaldehyde and the urea of low mol ratio, aftertreatment by formaldehyde activation and ammoniacal liquor, not only formaldehyde content is low, bonding strength is high for the urea-formaldehyde resin of feasible preparation, and cost is low.
For achieving the above object, urea-formaldehyde resin of the present invention adopts the following steps preparation:
1) formaldehyde is added reactor after, be 3-4 with sour adjust pH;
2) under 50 ± 5 ℃, make formaldehyde activation 15-25 minute, add first urea then, the mol ratio that makes urea and formaldehyde is 1: 1.9-2.2, keep reaction 20-30 minute at 50 ± 5 ℃;
3) with lye pH adjustment to 7.2-7.8, add second batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.4-1.6;
4) in 30-40 minute, be warming up to 90 ± 5 ℃, reacted 40-60 minute;
5) with the acid solution adjust pH to 4-6, continue to react to viscosity: 25 ℃, be coated with-4 glasss of 22-26 seconds;
6) with the lye pH adjustment value to 7.0-7.5, add the 3rd batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.2-1.4,90 ± 5 ℃ of down reactions 20-30 minute;
7) cool to 70 ± 5 ℃, add the 4th batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.0-1.1, reacted 30 minutes;
8) add ammoniacal liquor,, cool to below 40 ℃ discharging then 60 ℃ of insulations 20-30 minute.
Wherein, the concentration of formaldehyde is 37%; The acid of using in the step 1) is selected from one or more in sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, the acetate; The alkali that uses is selected from one or more in sodium hydroxide, potassium hydroxide, yellow soda ash, the trolamine; The concentration of ammoniacal liquor is 25%, and the consumption of ammoniacal liquor is the 5-7% of urea gross weight, is preferably 6%.
The advantage of the inventive method:
Adopted in 1 the inventive method by the activation of formaldehyde and the step of last ammonia treatment, because formaldehyde activates under acidic conditions and becomes
+C
2OH has improved and amino reactive activity; The processing of last ammoniacal liquor makes most of free formaldehyde reaction generate hexamethylenetetramine, therefore, has lower formaldehyde content by synthetic urea-formaldehyde resin of the present invention, and the free formaldehyde content of the bright synthetic urea-formaldehyde resin of detected result is below 0.1%;
2 is under the situation of 1.0-1.1 at raw material formaldehyde and urea mol ratio, and the Joint strength that the performance of the urea-formaldehyde resin adhesive of production is very high can make the bonding strength of cementitious wood-based panel product be up to state standards;
Do not add any properties-correcting agent in 3 the inventive method, do not dewater, so manufacturing process is simple, cost is low.
Embodiment
Embodiment one
Composition of raw materials:
| Raw material | Mol ratio | Content (%) | Weight part | Remarks |
| Urea formadehyde ammoniacal liquor formic acid NaOH | 1.08 1 | 37 100 25 30 30 | 146.1 100 6 is an amount of | U1=51.4 part U2=16.1 part U3=10.0 part U4=22.5 part is regulated pH value and is regulated pH value |
By urea and formaldehyde mole ratio is to get the raw materials ready at 1: 1.08, and reactions steps comprises:
1) 37% industrial formol, 146.1 weight parts being added reactor, is 3.2-3.4 with the formic acid adjust pH;
2) be heated to 50 ℃, make formaldehyde activation 20 minutes, add first urea 51.4 weight parts then, 50 ℃ of reactions 20 minutes;
3) use the sodium hydroxide adjust pH to 7.2-7.8, add second batch of urea 16.1 weight part;
4) in 20 minutes, be warming up to 90 ℃, be incubated 60 minutes;
5) with the formic acid adjust pH to 4.2-4.8, react to viscosity: 25 ℃, be coated with-4 glasss of 22-26 seconds;
6) use the sodium hydroxide adjust pH to 7.0-7.5, add the 3rd batch of urea 10.0 weight parts, 90 ℃ were reacted 20 minutes;
7) cool to 70 ℃, add urea 22.5 weight parts of the 4th batch of residual content, reacted 30 minutes;
8) adding concentration is 25% industrial ammonia 6 weight parts, 60 ℃ of insulations 20 minutes down, cools to below 40 ℃ discharging.
The resin quality index:
Solids content 56-62%
PH value 8.0-8.5
Viscosity (20 ℃) 150-300mPas
Curing speed 70-90 second
Free formaldehyde content＜0.1%
Working life＞4 hour
30-60 days storage period
Comparative example one
Composition of raw materials:
| Raw material | Mol ratio | Content % | Weight part | Remarks |
| Urea formadehyde formic acid sodium hydroxide | 1.08 1 | 37 100 30 30 | 146.1 100 is an amount of | U1=51.4 part U2=16.1 part U3=32.5 part is regulated pH value and is regulated pH value |
By urea and formaldehyde mole ratio is to get the raw materials ready at 1: 1.08, and reactions steps is as follows:
1) 37% industrial formol, 146.1 weight parts is added reactor, transfer pH=7.2-7.8 with sodium hydroxide;
2) add first urea 51.4 weight parts;
3) in 35 minutes, be warming up to 90 ℃, be incubated 60 minutes;
4) with the formic acid adjust pH to 4.2-4.8, react to viscosity: 25 ℃, be coated with-4 glasss of 22-26 seconds;
5) use the sodium hydroxide adjust pH to 7.0-7.5, add second batch of urea 16.1 weight part, 90 ℃ of reactions 20 minutes;
6) cool to 70 ℃, add urea 32.5 weight parts of the 3rd batch of residual content, reacted 30 minutes;
7) cool to 40 ℃, discharging.
The resin quality index:
Solids content 56-62%
PH value 7.0-7.5
Viscosity (20 ℃) 150-300mPas
Curing speed 80-100 second
Free formaldehyde content＜0.2%
Working life＞4 hour
15-30 days storage period
Experimental example one
Adopt the urea-formaldehyde resin of producing by embodiment one method and comparative example one method to prepare three-ply-wood and five-ply board respectively.Wherein, the preparation technology that three-ply-wood and five-ply board adopted is: during impregnation, add the flour of urea-formaldehyde resin weight 10%, 0.5% ammonium chloride in urea-formaldehyde resin; Veneer is 10 years living board using poplar boards; Heat pressing process is: pressure 1.0-1.5MPa, temperature: 100-115 ℃; Time: 40s/mm.
Utilize the detected result of the glued board that the urea-formaldehyde resin adhesive of the low formaldehyde content high-performance urea-formaldehyde resin adhesive of the embodiment of the invention one and comparative example one makes as shown in table 1.Wherein, measure burst size of methanal, press the regulation of GB/T17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " and measure bonding strength with the moisture eliminator method.
Table 1
| Test specimen | Burst size of methanal (mg/L) | Bonding strength (MPa) | ||
| Embodiment one | Comparative example one | Embodiment one | Comparative example one | |
| Three-ply-wood | 0.65 | 2.3 | 0.91 | 0.72 |
| Five-ply board | 0.86 | 2.6 | 0.87 | 0.73 |
Embodiment two
Composition of raw materials:
| Raw material | Mol ratio | Content (%) | Weight part | Remarks |
| Urea formadehyde ammoniacal liquor formic acid NaOH | 1.008 1 | 37 25 30 30 | 136.2 100 5 is an amount of | U1=50.1 part U2=12.9 part U3=9.0 part U4=28.0 part is regulated pH value and is regulated pH value |
Concrete reactions steps comprises:
1) 37% industrial formol, 136.2 weight parts being added reactor, is 3.5-4.0 with the formic acid adjust pH;
2) be heated to 50 ℃, make formaldehyde activation 20 minutes, add first urea 50.1 weight parts then, 50 ℃ of reactions 20 minutes;
3) use the sodium hydroxide adjust pH to 7.2-7.8, add second batch of urea 12.9 weight part;
4) in 22 minutes, be warming up to 90 ℃, be incubated 60 minutes;
5) with the formic acid adjust pH to 5.2-5.8, react to viscosity: 25 ℃, be coated with-4 glasss of 22-26 seconds;
6) use the sodium hydroxide adjust pH to 7.0-7.5, add the 3rd batch of urea 9.0 weight parts, reacted 20 minutes down at 90 ℃;
7) cool to 70 ℃, add urea 28.0 weight parts of the 4th batch of residual content, reacted 30 minutes;
8) adding concentration is 25% industrial ammonia 5 weight parts, and 60 ℃ of insulations 20 minutes cool to below 40 ℃ discharging.
The resin quality index:
Solids content 58-63%
PH value 8.0-8.5
Viscosity (20 ℃) 150-300mPas
Curing speed 80-100 second
Free formaldehyde content＜0.05%
Working life＞4 hour
30-60 days storage period
Comparative example two
Proportioning raw materials:
| Raw material | Mol ratio | Content % | Weight part | Remarks |
| Urea formadehyde formic acid sodium hydroxide | 1.008 1 | 37 30 30 | 136.2 100 is an amount of | U1=50.1 part U2=12.9 part U3=37 part is regulated pH value and is regulated pH value |
Concrete reactions steps comprises:
1) 37% industrial formol, 136.2 weight parts is added reactor, transfer pH=7.2-7.8 with sodium hydroxide;
2) add first urea 50.1 weight parts;
3) in 35 minutes, be warming up to 90 ℃, be incubated 60 minutes;
4) with the formic acid adjust pH to 4.2-4.8, react to viscosity: 25 ℃, be coated with-4 glasss of 22-26 seconds;
5) use the sodium hydroxide adjust pH to 7.0-7.5, add second batch of urea 12.9 weight part, 90 ℃ were reacted 20 minutes;
6) cool to 70 ℃, add the 3rd batch of residual content urea 37 weight parts, reacted 30 minutes;
7) cool to below 40 ℃ discharging.
The resin quality index:
Solids content 58-63%
PH value 7.0-7.5
Viscosity (20 ℃) 150-300mPas
Curing speed 120-150 second
Free formaldehyde content＜0.15%
Working life＞4 hour
15-30 days storage period
Experimental example two
The urea-formaldehyde resin that adopts embodiment two methods and comparative example two methods to produce respectively prepares three-ply-wood and five-ply board, and the technological process of preparation three-ply-wood and five-ply board is identical with experimental example one with condition.
The burst size of methanal of each glued board and the detected result of bonding strength see Table 2.Wherein, measure burst size of methanal, press the regulation of GB/T17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " and measure bonding strength with the moisture eliminator method.
Table 2
| Test specimen | Burst size of methanal mg/L | Bonding strength MPa | ||
| Embodiment two | Comparative example two | Embodiment two | Comparative example two | |
| Three-ply-wood | 0.33 | 1.34 | 0.81 | 0.32 |
| Five-ply board | 0.51 | 1.72 | 0.83 | 0.38 |
As seen table 1 and table 2 though the bonding strength of comparative example 1 is higher, are respectively three-ply-wood 0.81MPa, five-ply board 0.83MPa thus, and its burst size of methanal is also higher, is respectively three-ply-wood 2.3mg/L, five-ply board 2.6mg/L; Though and comparative example 2 burst size of methanal have reduced, be respectively three-ply-wood 1.34mg/L, five-ply board 1.72mg/L, its bonding strength also obviously reduces simultaneously, only is three-ply-wood 0.32MPa, five-ply board 0.38MPa, well below national standard (0.7MPa).
In contrast, not only burst size of methanal is very low to utilize the cementitious glued board product of urea-formaldehyde resin adhesive of the inventive method preparation, all can satisfy national E1 level (being not more than 1.5mg/L) standard, even can reach or near the requirement of European E0 level (being not more than 0.5mg/L), and product still kept higher bonding strength, is up to state standards more than (0.7MPa).
Claims (10)
1, a kind of urea-formaldehyde resin is characterized in that making according to following steps (a) to (h) order:
(a) formaldehyde is added reactor after, be 3-4 with sour adjust pH;
(b) under 50 ± 5 ℃, make formaldehyde activation 15-25 minute, add first urea then, the mol ratio that makes urea and formaldehyde is 1: 1.9-2.2, keep reaction 20-30 minute at 50 ± 5 ℃;
(c) with lye pH adjustment to 7.2-7.8, add second batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.4-1.6;
(d) in 30-40 minute, be warming up to 90 ± 5 ℃, reacted 40-60 minute;
(e) with the acid solution adjust pH to 4-6, continue to react to viscosity: 25 ℃, be coated with-4 glasss of 22-26 seconds;
(f) with the lye pH adjustment value to 7.0-7.5, add the 3rd batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.2-1.4,90 ± 5 ℃ of down reactions 20-30 minute;
(g) cool to 70 ± 5 ℃, add the 4th batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.0-1.1, reacted 30 minutes;
(h) add ammoniacal liquor,, cool to below 40 ℃ discharging then 60 ℃ of insulations 20-30 minute.
2, urea-formaldehyde resin as claimed in claim 1 is characterized in that: in described step (b), under 50 ℃, make formaldehyde activation 20 minutes.
3, urea-formaldehyde resin as claimed in claim 1, the concentration that it is characterized in that described ammoniacal liquor is 25%, the consumption of ammoniacal liquor is the 5-7% of urea gross weight.
4, as the arbitrary described urea-formaldehyde resin of claim 1 to 3, it is characterized in that acid in the described step a) is selected from one or more in sulfuric acid, hydrochloric acid, phosphoric acid, the formic acid, described alkali is selected from one or more in sodium hydroxide, potassium hydroxide, yellow soda ash, the trolamine.
5, according to the arbitrary described urea-formaldehyde resin of claim 1 to 3, it is characterized in that:
In described step (b), the mol ratio that makes described urea and described formaldehyde is 1: 2.01,
In described step (c), the mol ratio that makes described urea and formaldehyde is 1: 1.6;
In described step (f), the mol ratio that makes described urea and formaldehyde is 1: 1.4;
In described step (g), the mol ratio that makes described urea and formaldehyde is 1: 1.08.
6, a kind of preparation method of urea-formaldehyde resin, (a) to (h) order is made according to the following steps:
(a) formaldehyde is added reactor after, be 3-4 with sour adjust pH;
(b) under 50 ± 5 ℃, make formaldehyde activation 15-25 minute, add first urea then, the mol ratio that makes urea and formaldehyde is 1: 1.9-2.2, keep reaction 20-30 minute at 50 ± 5 ℃;
(c) with lye pH adjustment to 7.2-7.8, add second batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.4-1.6;
(d) in 30-40 minute, be warming up to 90 ± 5 ℃, reacted 40-60 minute;
(e) with the acid solution adjust pH to 4-6, continue to react to viscosity: 25 ℃, be coated with-4 glasss of 22-26 seconds;
(f) with the lye pH adjustment value to 7.0-7.5, add the 3rd batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.2-1.4,90 ± 5 ℃ of down reactions 20-30 minute;
(g) cool to 70 ± 5 ℃, add the 4th batch of urea, the mol ratio that makes urea and formaldehyde is 1: 1.0-1.1, reacted 30 minutes;
(h) add ammoniacal liquor,, cool to below 40 ℃ discharging then 60 ℃ of insulations 20-30 minute.
7, the preparation method of urea-formaldehyde resin as claimed in claim 6 is characterized in that: in described step (b), under 50 ℃, make formaldehyde activation 20 minutes.
8, the preparation method of urea-formaldehyde resin as claimed in claim 6, the concentration that it is characterized in that described ammoniacal liquor is 25%, the consumption of ammoniacal liquor is the 5-7% of urea gross weight.
9, as the preparation method of the arbitrary described urea-formaldehyde resin of claim 6 to 8, it is characterized in that acid in the described step a) is selected from one or more in sulfuric acid, hydrochloric acid, phosphoric acid, the formic acid, described alkali is selected from one or more in sodium hydroxide, potassium hydroxide, yellow soda ash, the trolamine;
10, according to the preparation method of the arbitrary described urea-formaldehyde resin of claim 6 to 8, it is characterized in that:
In described step (b), the mol ratio that makes described urea and described formaldehyde is 1: 2.01,
In described step (c), the mol ratio that makes described urea and formaldehyde is 1: 1.6;
In described step (f), the mol ratio that makes described urea and formaldehyde is 1: 1.4;
In described step (g), the mol ratio that makes described urea and formaldehyde is 1: 1.08.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100598434A CN100384899C (en) | 2006-03-15 | 2006-03-15 | Urea resin and production thereof |
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|---|---|---|---|
| CNB2006100598434A CN100384899C (en) | 2006-03-15 | 2006-03-15 | Urea resin and production thereof |
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| CN1817932A true CN1817932A (en) | 2006-08-16 |
| CN100384899C CN100384899C (en) | 2008-04-30 |
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| CNB2006100598434A Expired - Fee Related CN100384899C (en) | 2006-03-15 | 2006-03-15 | Urea resin and production thereof |
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| CN101134803B (en) * | 2007-08-23 | 2010-12-08 | 北京市农林科学院 | Urea-formaldehyde foam plant cultivation substrate and method for preparing the same |
| CN102504156A (en) * | 2011-10-13 | 2012-06-20 | 江苏大江木业集团有限公司 | Urea-formaldehyde resin and preparation method thereof |
| CN102585130A (en) * | 2012-02-20 | 2012-07-18 | 常州大学 | Urea-formaldehyde resin adhesive produced by taking amino acid as formaldehyde catcher and preparation method thereof |
| CN102775946A (en) * | 2012-07-18 | 2012-11-14 | 广西华峰林业股份有限公司 | MDF(Medium-density fiber)-E1-level urea-formaldehyde resin adhesive |
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| CN104513640A (en) * | 2013-12-15 | 2015-04-15 | 广西鹿寨通用人造板有限公司 | Preparation method of urea formaldehyde glue |
| CN110359117A (en) * | 2019-07-30 | 2019-10-22 | 中原工学院 | A kind of preparation method of ureaformaldehyde fiber |
| CN110643384A (en) * | 2018-06-26 | 2020-01-03 | 宝山钢铁股份有限公司 | Synthesis and use method of coke making blended coal colloid additive |
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| CN1115369C (en) * | 1998-07-31 | 2003-07-23 | 杭州阳光文化用品有限公司 | Process for preparing adhesive of urea-formaldehyde resin |
| CN1311281A (en) * | 2001-02-09 | 2001-09-05 | 季维庆 | Process for producing environment protection solid urea-formaldehyde glue powder |
| 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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| CN102504156A (en) * | 2011-10-13 | 2012-06-20 | 江苏大江木业集团有限公司 | Urea-formaldehyde resin and preparation method thereof |
| CN102504156B (en) * | 2011-10-13 | 2013-03-20 | 江苏大江木业集团有限公司 | Urea-formaldehyde resin and preparation method thereof |
| CN102585130B (en) * | 2012-02-20 | 2014-10-29 | 常州大学 | Urea-formaldehyde resin adhesive produced by taking amino acid as formaldehyde catcher and preparation method thereof |
| CN102585130A (en) * | 2012-02-20 | 2012-07-18 | 常州大学 | Urea-formaldehyde resin adhesive produced by taking amino acid as formaldehyde catcher and preparation method thereof |
| CN102775946A (en) * | 2012-07-18 | 2012-11-14 | 广西华峰林业股份有限公司 | MDF(Medium-density fiber)-E1-level urea-formaldehyde resin adhesive |
| CN103214312A (en) * | 2013-04-25 | 2013-07-24 | 黄河水利委员会黄河水利科学研究院 | High-molar-ratio urea formaldehyde slow-release fertilizer and preparation method for same |
| CN103214312B (en) * | 2013-04-25 | 2014-12-24 | 黄河水利委员会黄河水利科学研究院 | High-molar-ratio urea formaldehyde slow-release fertilizer and preparation method for same |
| CN103465336A (en) * | 2013-10-09 | 2013-12-25 | 赤水市新生竹纤维板有限公司 | Method for producing bamboo particle board by using bamboo shavings |
| CN104513640A (en) * | 2013-12-15 | 2015-04-15 | 广西鹿寨通用人造板有限公司 | Preparation method of urea formaldehyde glue |
| CN104513640B (en) * | 2013-12-15 | 2016-09-07 | 广西鹿寨通用人造板有限公司 | The preparation method of urea formaldehyde glue |
| CN110643384A (en) * | 2018-06-26 | 2020-01-03 | 宝山钢铁股份有限公司 | Synthesis and use method of coke making blended coal colloid additive |
| CN110359117A (en) * | 2019-07-30 | 2019-10-22 | 中原工学院 | A kind of preparation method of ureaformaldehyde fiber |
| CN110359117B (en) * | 2019-07-30 | 2022-01-21 | 中原工学院 | Preparation method of urea-formaldehyde fiber |
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| CN100384899C (en) | 2008-04-30 |
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